Hydroformylation process employing diorgano-halo phosphines as legands with cobalt carbonyl

ABSTRACT

An Oxo process wherein an olefin is reacted with hydrogen and carbon monoxide in the presence of a cobalt carbonyl and a dialkyl halo phosphine or a diaryl halo phosphine, preferably in the presence of a trialkyl amine.

United States Patent Inventors John F. Dellner Glenshaw; Edmond R. 'luocl, Pittsburgh; John V. Ward, Oalrmont, all of Pa.

Appl. No. 574,298

Filed Aug. 23, 1966 Patented Nov. 30, 1971 Assignee Gull Research 8; Development Company Pittsburgh, Pa.

HYDROFORMYLATION PROCESS EMPLOYING DIORGANO-HALO PHOSPHINES AS LEGANDS [50] Field of Search 260/604 HF, 638 HF, 6l7 HF, 598 R, 632 HF Primary Examiner-Leon Zitver Assistant Examiner-R. H. Liles Anorneys- Meyer Neishloss, Deane E. Keith and Joseph .I.

Carducci ABSTRACT: An Oxo process wherein an olefin is reacted with hydrogen and carbon monoxide in the presence of a cobalt carbonyl and a dialkyl halo phosphine or a diaryl halo phosphine, preferably in the presence of a trialkyl amine.

HYDROFORMYLATION PROCESS EMPLOYING DlORGANO-HALO PHOSPHINES AS LEGANDS WITH COBALT CARBONYL This invention relates to an Oxo process or hydroformylation reaction, wherein hydrogen and carbon monoxide are added to an olefinic compound in the presence of a catalyst to obtain a mixture predominating in an aldehyde having one more carbon than said olefinic compound.

The catalyst generally employed for the hydroformylation reaction is a cobalt salt of a higher molecular weight fatty acid, such as octanoic, stearic, oleic, palmitic, naphthenic, etc. acids. Inorganic salts, such as cobalt carbonate, can also be employed. Most of these salts are soluble in most of the olefinic feeds supplied to the hydroformylation reaction zone, but when they are not, they can be supplied in an inert, liquid hydrocarbon in which they are soluble, such as benzene, xylenes, naphtha, heptane, decane, etc. Although the catalyst is supplied in the form of a cobalt salt to the hydroformylation reaction zone, under the conditions existing therein the salt reacts with carbon monoxide, preferably in the presence of hydrogen, to form a cobalt carbonyl, that is, one or more of the following: cobalt hydrocarbonyl, HCo(CO) dicobalt octacarbonyl, Co (C),; and/or tetracobalt dodecacarbonyl, Co,(CO), As defined herein, cobalt carbonyl will refer to any one or all of the specific cobalt carbonyls referred to above. It is generally believed that the cobalt carbonyl is the active form or catalyst for the hydroformylation reaction.

Since cobalt carbonyls are thermally unstable and will easily decompose to elemental cobalt and carbon monoxide, it is necessary to maintain a high pressure of hydrogen and carbon monoxide in the hydroformylation reaction zone to inhibit such decomposition at the elevated temperatures existing in the hydroformylation reaction zone. At the end of the reaction period, the reaction product will consist largely of an aldehyde having one carbon more than the olefinic charge, plus unreacted hydrogen and carbon monoxide and some alcohol, corresponding to the aldehyde, carrying dissolved cobalt car bonyl. The unreacted hydrogen and carbon monoxide can rather easily be separated from the reaction product, for example, by flash distillation, but the cobalt carbonyl is removed only with difficulty. It is obvious that if the aldehyde product, as such, is desired, it would be necessary to remove cobalt carbonyl therefrom. In most cases the aldehyde is subjected to hydrogenation conditions in the presence of a hydrogenation catalyst, such as nickel, to convert the aldehyde to the corresponding alcohol. In such case it becomes even more imperative to remove cobalt carbonyl from the aldehyde being hydrogenated, since at the lower pressures employed in the hydrogenation reactor cobalt carbonyl will decompose to cobalt and carbon monoxide, the latter being undesirable in the hydrogenation reaction zone, since it has a tendency to poison the hydrogenation catalyst, such as nickel, which is generally used.

It has been customary, therefore, to subject the hydroformylation reaction product to a decobalting operation to remove cobalt carbonyl therefrom. This has generally involved subjecting the hydroformylation reaction product to temperature and pressure conditions favoring the decomposition of cobalt carbonyl to elemental cobalt and carbon monoxide. Elemental cobalt is difficult to remove from the hydroformylation reaction product, and it has a tendency to plug the lines leading to and from the decobalter and for some to find its way into the hydrogenation reactor. The removal of such cobalt adds significantly to the overall cost of the hydroformylation reaction. Cobalt so obtained, in addition, has to be discarded or, by a tedious procedure may, perhaps, be converted back to the original cobalt salt or cobalt carbonyl or use in the hydroformylation reaction zone.

We have found, however, that the above difficulties can be avoided by employing in the hydroformylation reaction zone a cobalt catalyst, such as defined above, and a specific phosphine selected from the group consisting of a dialkyl halo phosphine and a diaryl halo phosphine having the following structural formula:

wherein R and R the same or different, is an alkyl substituent having from one to 16 carbon atoms, preferably from one to four carbon atoms, or an aryl substituent having from six to 16 carbon atoms, preferably from six to eight carbon atoms, and X is a halogen selected from the group consisting of fluorine, chlorine, bromine or iodine, preferably chlorine. Specific examples of alkyl substitutents are methyl, ethyl, npropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, isopropyl, 2-methylbu- 'tyl, 2-ethylpentyl, 3-butylhexyl, 4-pentyldecyl, 2,2-dimethyldecyl, 3-methyl-4-ethyldecyl, 5-propylhexyl, 3-methyldodecyl, o-ethyldodecyl, 3,3'-dimethyltetradecyl, 2-butylhexadecyl, etc., and of aryl substituents are phenyl, tolyl, xylyl, 1,3,5-trimethylphenyl, ethylphenyl, propylphenyl, butylphenyl, hexylphenyl, decylphenyl. dodecylphenyl, tetradecylphenyl, hexadecylphenyl, etc. Specific examples of dialkyl halo diaryl halo phosphines that can be employed herein include dimethylchlorophosphine, dimethylbromophosphine, dimethylfluorophosphine, di-n-propylchlorophosphine, di-nbutylchlorophosphine, di-n-butylbromophosphine, di-n-butylfluorophosphine, di-n-butyliodophosphine, di-n-pentylchlorophosphine, di-n-hexylchlorophosphine, di-ndecylchlorophosphine, di-n-hexadecylchlorophosphine, di(2- methylbutyl)chlorophosphine, di( 2-methylbutyl )bromophosphine, di(Z-ethylpentyl)chlorophosphine, di(B-methyldodecyl)chlorophosphine, di(3,3'-dimethyltetradecyl)chlorophosphine, diphenylchlorophosphine, diphenylbromophosphine, ditolylchlorophosphine, dixlylchlorophosphine, di( ethylphenyl )chlorophosphine, di(dodecylphenyl)fluorophosphine, di(hexadecylphenyl)iodophosphine, etc. We believe that under the hydroformylation reaction conditions, the dialkyl halo phosphine or the diaryl halo phosphine, as a ligand, combines with the cobalt carbonyl and fonns a complex therewith. By ligand" we intend to include a dialkyl halo phosphine or a diaryl halo phosphine which contains an element with an electron pair that can form a coordination compound with a metal compound.

While we are not absolutely certain, we have reasons to conclude that the complex formed between cobalt carbonyl and the above-defined dialkyl halo phosphines or diaryl halo phosphines can be expressed by the following structural formula:

vl )4l. wherein B is selected from the group consisting of dialkyl halo phosphines and diaryl halo phosphines, defined above, at and y are whole numbers from one to four and x+ =5. This complex is also a new composition of matter and forms part of the invention defined and claimed herein.

Although the complex defined above is thermally stable and can be used, as such, in a number of hydroformylation reactions without appreciable decomposition thereof, the complex can be rendered even more thermally stable by employing in admixture therewith a selected amount of a trialkyl amine having pK,, acidity of at least about +8 but no greater than about +15, preferably a pK,, acidity of about +10 to about +13. By "pK,, acidity" we mean to refer to the negative logarithm of the Bronsted acid dissociation constant. Weak bases have low pK,, values, while strong bases have high pK,, values. Although there may be some tendency for the trialkyl amine to complex with the cobalt carbonyl, we are of the opinion that only a small amount of such complexing takes place, since there is a greater tendency for a complex to form between cobalt carbonyl and the dialkyl halo phosphine or diaryl halo phosphine, as set forth above. To the extent that a complex forms between cobalt carbonyl and the above amine, the same can be defined in accordance with the following structural formula:

wherein x is a whole number from one to four, y is a whole number from one to four, x-l-y= and R is an alkyl substituent of the amine as defined below.

By trialkyl amine" that we employ herein for increased catalyst thermal stability, we intend to include those trialkyl amines whose individual alkyl substituents will have from one to 16 carbon atoms, preferably from one to about 12 carbon atoms, as well as those whose alkyl substituents carry one or more aldehydic, alcoholic, chlorine, fluorine or phenyl substituents thereon. Each of the individual alkyl substitutents attached to the nitrogen atom of the amine, moreover, does not have to be similar to another substituent on the same amine. Specific amines that can be employed herein include trimethylamine, tri-n-butylamine, tri-n-hexylamine, tri-ndodecylamine, tri-n-hexadecylamine, tribenzylamine, N,N- dimethylbenzylamine, N,N-dimethylnaphthylamine, N,N- methylbutylbenzylamine, N,N-butylethylbenzylamine, N,N- diethyldodecylamine, 2,2,2"-iminotriethanol, 2,2,2- iminotriethylchloride, 4,4'4"-iminotributylchloride, l ,l i iminotrimethylfiuoride, 4,4'4"-iminotributyraldehyde, 7,77" -iminotriheptaldehyde, etc.

The cobalt complex defined above, that is, the complex formed between cobalt carbonyl and the dialkyl halo phosphine or diaryl halo phosphine, is easily obtained and employed herein. in a preferred embodiment it is obtained in situ in the hydroformylation reaction zone. Thus, one of the cobalt salts, for example, one of those defined above, is introduced into the hydrofonnylation reaction zone along with one of the defined dialkyl halo phosphines or diaryl halo phosphines, the olefin to be subjected to hydroformylation reaction, hydrogen and carbon monoxide. Any olefinic compound that can be subjected to hydroformylation reaction and can be converted therein to aldehyde having one more carbon than said olefin can be employed. Representative examples of olefins that can be employed include propylene, butenel pentenel hexenel, heptene-l octenel decenel tetradecene-l, hexadecenel, pentene-2, hexene-2, heptene-Z, octene-2, 4-methyl-l-pentene, 2,4,4-trimethyl-l-pentene, 4-methyl-2-pentene, 2,6- dimethyl-3-heptene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 4-methyl-l-cyclohexene, etc. The molar ratio of hydrogen to carbon monoxide can be from about 5:1 to about 0.5:1, preferably from about 1:1 to about 2:1. The amount of hydrogen and carbon monoxide needed is at least that amount stoichiometrically required for addition to the olefinic compound, although from about 1% to about three times the amount stoichiometrically required can be employed. The amount of dialkyl halo phosphine or diaryl halo phosphine employed is from about 0.5 to about 10, preferably from about l to about 4 mols per mol of cobalt carbonyl. When an amine is employed, it is also introduced into the reaction zone. From about 0.5 to about 10, preferably from about 2 to about 4 mols of amine per mol of cobalt carbonyl can be employed.

The reaction conditions in the hydroformylation reaction zone can vary over a wide range. Thus, the temperature can be from about 150 to about 475 F., preferably from about 250 to about 400 F., while the pressure can be from about 500 to about 5,000 pounds per square inch gauge, preferably from about 1,000 to about 3,000 pounds per square inch gauge. Reaction time can be from about 5 minutes to about 5 hours, but preferably will be from about 30 minutes to l20 minutes.

As a result of the above, the cobalt salt will be converted to cobalt carbonyl and the latter, in turn, will complex with the dialkyl halo phosphine or the diaryl halo phosphine to form the new complex defined above, which becomes the hydroformylation reaction catalyst. At the end of the reaction period the converted product obtained will contain from about 50 to about 100 percent by weight of aldehyde having one more carbon than said olefinic charge and from about 2 to about 40 percent by weight of alcohol corresponding to said aldehyde. Also present with the converted product, of course, are unreacted hydrogen and carbon monoxide but also the cobalt carbonyl-dialkyl halo phosphine or the cobalt carbonyl-diaryl halo phosphine complex and the trialkyl amine, when the latter is also employed. The unreacted hydrogen and carbon monoxide can be recovered from the reaction product in any convenient manner, for example, by flashing at a temperature of about to about 100 C. and a pressure of about l5 to about 500 pounds per square inch gauge. The aldehyde and alcohol present in the resulting reaction product can be removed therefrom in any convenient manner, for example, by subjecting the resulting reaction mixture to a temperature of about to about 200 C. and a pressure of about 0.001 to about 760 millimeters absolute pressure. As a result of such action the aldehyde and alcohol are flashed off together or separately and left behind is the cobalt catalyst complex, trialkyl amine and/or solvent, when used and a small amount of polymerization product, which can be primarily acetals, hemiacetals and esters. A feature of the present process is that less polymer is formed herein than is generally formed during the conventional hydroformylation reaction process wherein uncomplexed cobalt carbonyl is employed as catalyst. Another additional, and quite important feature of the present process, is that the ratio of normal aldehyde and/or normal alcohol to iso aldehyde and/or iso alcohol is very high, from about 4:1 to about 8:]. Normal aldehydes and/or normal alcohols are highly desirably commercially. Thus, normal aldehydes can be aldolized to yield 2-ethylhexanol which is useful as a plasticizer, or they can be hydrogenated to normal alcohols which are useful as commercial solvents or plasticizers. The cobalt carbonyl complex herein, along with the trialkyl amine, when used, can be recovered from the polymer in any convenient manner, for example, by ion-exchange, solvent extraction or distillation, or can be permitted to remain in combination with the polymer, which can serve as solvent therefor, and can be reused during the hydroformylation reaction as previously defined. This procedure can be repeated many times, since the cobalt carbonyl complex defined herein is stable and will not decompose under the reaction and recovery conditions employed herein.

The cobalt carbonyl complex catalyst need not be formed in situ, as defined above, but can be preformed. Thus, a mixture of cobalt carbonyl, such as defined above, can be combined with one of the dialkyl halo phosphines or diaryl halo phosphines, preferably in an inert solvent such as benzene, xylene, naphtha, heptane, decane, etc., at a temperature of about 30 to about 250 C., preferably about 25,to about 150 C., and a pressure of about 15 to about 5,000 pounds per square inch gauge, preferably about 15 to about pounds per square inch gauge for about 1 to about minutes, preferably for about 10 to about 30 minutes. lf an amine is to be used in combination with the complex so formed, it can be added to the mixture along with the dialkyl halo phosphine or the diaryl halo phosphine, or it can be added to the complex in the hydroformylation reaction zone. If desired, the cobalt carbonyl complex can be obtained as defined immediately above by substituting one of the previously defined cobalt salts for the cobalt carbonyl. In such case, however, at least about I to about 20 mols of carbon monoxide, preferably about I to about 8 mols of carbon monoxide, relative to the cobalt salt must also be present. The resulting mixture can be used as such in the hydroformylation reaction zone as catalyst, or if desired the cobalt carbonyl complex can be recovered from the mixture in any suitable manner, for example, by ionexchange, solvent extraction or distillation.

The process of this invention can further be illustrated by the following:

EXAMPLE I A series of runs were made wherein olefins were subjected to hydroformylation reaction in the presence of the cobalt carbonyl complex defined above. Thus, into a 500 milliliter stainless steel autoclave there was placed I00 milliliters of benzene and l 1 grams of a solution containing 8 milliliters of benzene and 4 grams of the cobalt salt of 2-ethylhexanoic acid. The autoclave was flushed with nitrogen gas and then pressured with synthesis gas containing 1.2 mols of hydrogen per mol of carbon monoxide to a pressure of 300 pounds per square inch gauge. The autoclave was depressured to atmospheric pres- EXAMPLE lll In order to show that the catalyst complex defined herein is not only an effective hydroformylation reaction catalyst but sure and repressured with synthesis gas several times. The au- 5 that it can be recovered. as Such. at the end of the hy r rtoclave was finally pressured with synthesis gas to about 2,300 mylation reactionand can be reused for additional hydrofor- Pounds per square i h gauge at room temperature d h mylation reactions, two series of runs were made. In the first heated to 350 F. within 75 to 90 minutes. A temperature of Series of Yeponed in able 1v below, the y y 3500 and a pressure oL500 pounds were maintained for 1 lo tron reactions were carried out as 111 example 1, above, and hour. The autoclave was cooled to 120 F. and thereafter there Y r? employed mmlmols dicoba" om'carbonyl Slowly depressured to atmospheric pressum 100 milliliters of benzene, 1.43 mols of propylene, hydrogen To the dicobah oclacarbonyl thus formed in the autoclave and carbon monoxide having a molar ratio of 1.2: l tri-n-butyl there was added a dialkyl halo phosphine to be complexed angle gg i gg ggtf gis: ggz gfi g t gi fl firg therewith, a trialkyl amine, when used, hydrogen and carbon 0c car y y P P u g monoxide in a molar ratio of 1 21 and the oefin The reaction 3.8: 1 molar ratio with the dicobalt octacarbonyl. The pressure d t f l t was maintained at 3,500 pounds per square inch gauge, the mmure a h y relic temperature 320 F. and the reaction time 60 minutes. in the l"? an Pressure or 1 our to obtam a reacuon Product second series, reported in table V below, of runs the same concomam'ng substamlal amoums of an aldehyde havmg 9 siderations applicable to the first series were maintained excarbon than the reactant f f the conespondmg cept that 0.19 mol of propylene was employed and the presalcohol. At the end of the reaction period the autoclave was sure employed was 1 000 pounds squal-e i h gauge, cooled to about 75 F. and then depressured to atmospheric At h e d f the reaction period, the autoclave was cooled pressure and the product analyzed for its composition. The to 75 F. and depressured through two liquid nitrogen cold f sultsg lain d are tabulated below In tables 1 and traps and a gas meter. At atmospheric pressure the autoclave TABLE I Run Number Temperature, F 320 310 320 320 320 320 820 Pressure, p.s.i.g. 3,500 3,500 3,500 3,500 3,600 3,600 3,500 Residence time, minutes" 60 60 60 60 60 60 60 Benzene, grams 78 78 78 78 78 78 78 Propylene, grams. 00 60 60 60 60 60 ($0 Dicobalt octacnrbonyl, grams 2. 0 2. 0 2. 0 2.0 2. 0 2.0 2. 0 Tri-n-butylmuino, grams None 1.0 3. .l 7. 8 7. 8 3. 9 7, 3 Dibutyl chloro phos hine, grmns.. 1.5 1.5 1.6 1.5 3.0 4.0 0.0 Selectivity to norms product (aldehyde and alcohol, percent) 73.4 81. 9 85.0 86.4 87. 1 86.6 Conversion, percent 71. 3 60.7 38.6 30.4 20. 8 37.0 25. 2

TABLE 11 Run number Temperature, F. 320 320 320 320 320 320 235 Pressure, p.s.i.g 1,000 1,000 1,000 1,000 600 1,000 3, 1500 Residence time, minutes 60 60 60 60 60 60 60 Benzene, grams 8 78 78 78 78 78 78 olefimsrams 8.0 8.0 8.0 1&0 1g 0 160 Dicobalt octacarbunyl, gr ms 2, 0 2, 0 z 0 0 2. 0 2 0 20 Alkylamine,grams 3-9 4.5 4.6 4.6 3.0 4.6 Dibutyl chlorophosphlne, gr ms 4- 0 4. 0 4.0 4.0 4. 0 4. 0 1. 0 Selectivity to normal product (aldehyde and alcohol), percent... 87. 7 86.0 87. 0 70. 6 86. 5 87. 2 83. 0 Conversion. Percent 83.0 72. 9 73. o 72. 9 3 4 20, 2 n 5 1 Propylene.

3 Hexcned.

3 Tri-n-butyl amine.

4 Trim-beryl amine.

I N,N-dimcthyl benzene amino,

7 EXAMPLE ii Y was placed in a heated bath maintained at 158 F. and the pressure was slowly reduced to 50 millimeters of mercury absolute pressure. Volatile products as they were removed were collected in cold traps. When most of the product had distilled over, the autoclave was purged with nitrogen gas, and this was continued until no significant condensation occurred in the TABLE 111 Run Number Temperature, F 320 320 320 320 320 320 Pressure, p.s.i.g 1, 000 1, 000 l, 000 3, 600 3, 600 3, 600 Residence time, minutes. 60 60 60 60 60 60 Benzene, grams 78 78 78 78 78 78 Propylene, grams 8. 0 8. 0 8. 0 60 60 60 Dlcobalt octacarbonyl, grams 2.0 2.0 2.0 2. 0 2.0 2. 0 'Iri-n-butyl amine, grams... 3. 9 3. 9 3. 9 3. 9 3. 0 3. 9 Phosphine, grams 1 4.0 2 2. 2 3 4. 0 4 4.0 5 4.0 3 4. 0 Selectivity to normal product (aldehyde and alcohol), percent.-. 87. 9 78. 3 8i. 0 72. 3 Conversion, percent 73. 0 93. 5 82. 5 5

1 Dibutyl chloro phosphines. 1 Dibutyl bromo phosphine.

B Diphenyl chloro phosphine. 4 Phenyl dichloro phosphine. 5 Diethoxy chloro phosphine. 6 No reaction.

cold traps. The autoclave was repressured to atmospheric pressure with nitrogen, removed from the bath and chromatograph samples of the remaining product were taken to deter-' mine whether all C products had been re m oved therefrom.

The percent conversion of propylene to aldehyde and alcohol 5 and the selectivity of the olefin to normal aldehyde and normal alcohol were determined by subjecting the products in the cold traps to chromatographic analysis; The results are tabulated below in tables IV and V.

2. The process of claim 1 wherein said phosphine is a dialkyl halo phosphine.

3. The process of claim 1 wherein said phosphine isa diaryl halo phosphine. V

TABLE IV Molar percent Normal to iso Selectivity weight ratio Normal Normal Conto normal llydrolormylatlon Iso C4 C4 150 C4 04 version, aldehyde Aldercactlon N o. aldehyde aldehyde alcohol alcohol percent and alcohol hyde Alcohol 11. 41 77. 12 1. 47 10. 0O 37 87 6. 8 6. 8 11. 04 76. 84 1. 69 10. 53 38 87 7. 0 6. 6 11. 68 78. 36 1. 26 8. 81 38 87 6. 8 7. 0 11. 57 78. 76 1. 8. 48 37 87 6. 8 7. 1 12. 88 7d. 64 1. 82 11. 66 45 85 5. 7 6. 4 12. 85 78. 06 r i. 27 7. 82 49 86 6. 1 6. 1

Thermo couple trouble, slight temperature runaway.

TABLE V Molar percent Normal to iso Selectivity weight ratio Normal Normal Conto normal Hydroformylatlon Iso C4 04 I50 04 C4 version, aldehyde Aldereaction N o. dehyde aldehyde alcohol alcohol percent and alcohol hyde Alcohol 1. 9. 32 68. 24 3. 04 19. 40 63 88 7. 6. 4 2 ll. 11 67. 29 3. 08 18. 52 62 86 6. 1 6.0 10. 36 68. 22 3. 08 18. 33 71 87 6. 6 6. 0 9. 81 67. 3. 14 19. 70 70 87 6. J 6. 3 10. 19 66. 09 3. 08 20. 64 69 87 6. 6 6. 7 6 10. 86 66. 69 3. 26 19. 29 70 86 6. 1 5. 9

The data in tables IV and V show that the catalyst system can be reused many times during the hydroformylation reaction without decomposing to produce a desired product having a high normal to iso product (aldehyde and alcohol) ratio. The data additionally show that at low pressures at which conventional hydroformylation reaction catalysts have a tendencs to decompose to cobalt and carbon monoxide that is, at 1,00

pounds per square inch gauge, the present catalyst can be reused with excellent results.

Obviously many modifications and variations of the invention, as hereinabove set forth, can be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

4. The process of claim 1 wherein said phosphine is a dialkyl chloro phosphine.

5. The process of claim 1 wherein said phosphine is a diaryl chloro phosphine.

6. The process of claim 1 wherein said phosphine is dibutyl chloro phosphine 7. The process of claim 1 wherein said phosphine is dibutyl bromo phosphine.

8. The process of claim 1 wherein said phosphine is diphenyl chloro phosphine.

9. The process of claim 1 wherein the reaction is carried out in the additional presence of tri-n-butyl amine.

10. The process of claim 1 wherein the reaction is carried out in the additional presence of tri-n-hexyl amine.

11. The process of claim 1 wherein the reaction is carried out in the additional presence of N,N-dimethyl benzyl amine.

12. The process of claim I wherein the olefin is'propylene.

13. The process of claim 1 wherein said catalyst is recovered and reused in a subsequent hydroformylation reaction.

14. The process of claim 1 wherein the cobalt carbonyl is dicobalt octacarbonyl.

l l t 22 g UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,624, 1 Dated November 30, 1971 Inventor-(5) John F. Deffner, Edmond R. Tucci and John V. Ward It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 28, cancel "or" and replace with "of".

Column 1, line 69, cancel "or" and replace with "for".

Column 2, line 21, after "halo" insert "phosphines and".

Column 5, Footnote 5 of Table II, "N, N-dimethylbenzene amine" should read "N, N-dimethyl benzyl amine".

Column 5, Table III, under Footnote "1", "phosphines" should be changed to "phosphine" Column 5, Table III, under Run No. 20, reference number "3" should be changed to reference number "6". Below the Table, Footnote "6" should be changed from "No Reaction" to "Diphenoxy Chloro Phosphine". A Footnote "7" should then be added and designated as "No Reaction".

Signed and sealed this 3rd day of October- 1972.

(SEAL) Attest:

EDWARD E LFLETCPERJR. ROBERT GOTTSCHALK Attesting Officer- Commissioner of Patents 

2. The process of claim 1 wherein said phosphine is a dialkyl halo phosphine.
 3. The process of claim 1 wherein said phosphine is a diaryl halo phosphine.
 4. The process of claim 1 wherein said phosphine is a dialkyl chloro phosphine.
 5. The process of claim 1 wherein said phosphine is a diaryl chloro phosphine.
 6. The process of claim 1 wherein said phosphine is dibutyl chloro phosphine
 7. The process of claim 1 wherein said phosphine is dibutyl bromo phosphine.
 8. The process of claim 1 wherein said phosphine is diphenyl chloro phosphine.
 9. The process of claim 1 wherein the reaction is carried out in the additional presence of tri-n-butyl amine.
 10. The process of claim 1 wherein the reaction is carried out in the additional presence of tri-n-hexyl amine.
 11. The process of claim 1 wherein the reaction is carried out in the additional presence of N,N-dimethyl benzyl amine.
 12. The process of claim 1 wherein the olefin is propylene.
 13. The process of claim 1 wherein said catalyst is recovered and reused in a subsequent hydroformylation reaction.
 14. The process of claim 1 wherein the cobalt carbonyl is dicobalt octacarbonyl. 